A highly uniform thin protective coating, with good appearance, anti-corrosion properties and adhesion properties, is provided by a surface treatment method wherein a surface treatment solution for aluminum and its alloys is prepared using a surface treatment composition for aluminum and its alloys comprising at least one type of phosphoric acid, condensed phosphoric acid or salt of these acids, at least one type of zirconium salt or titanium salt and effective fluoride, further comprising at least one type of phosphorous acid, hypophosphorous acid or salts of these acids, and this solution is brought in contact with the surface of an aluminum type metal.
|
1. A surface treatment composition for aluminum and its alloys comprising at least one member selected from the group of phosphoric acid, condensed phosphoric acid or salt of said acids, at a concentration in the range of 10-500 ppm as PO4,
at least one member selected from the group of zirconium salt and titanium salt at a concentration in the range of 10-500 ppm as the metal, and effective fluoride, at a concentration in the range of 1-50 ppm as fluorine, further comprising at least one member selected from the group of phosphorous acid, hypophosphorous acid or salts of said acids, at a concentration in the range of 10-5000 ppm as PO3 or hypophosphorous acid.
2. A surface treatment solution for aluminum and its alloys as defined in
at least one type of zirconium salt or titanium salt, the concentration of said salt lying in the range 10-100 ppm as the metal, effective fluoride, the concentration of said fluoride lying in the range 3-50 ppm as fluorine, and at least one type of phosphorous acid, hypophosphorous acid or salt of said acids, the concentration of said acids or salts lying in the range 50-500 ppm as PO3 or hypophosphorous acid.
3. A surface treatment solution for aluminum and its alloys as defined in
at least one type of zirconium salt or titanium salt, the concentration of said salt lying in the range 10-100 ppm as the metal, effective fluoride, the concentration of said fluoride lying in the range 3-20 ppm as fluorine, and at least one type of phosphorous acid, hypophosphorous acid or salt of said acids, the concentration of said acids or salts lying in the range 50-500 ppm as PO3 or hypophosphorous acid.
|
|||||||||||||||||||||||||||||
1. Field of the Invention
This invention relates to a surface treatment composition for aluminum and its alloys, treatment solution and treatment method for aluminum and its alloys, and in particular, to a surface treatment composition, treatment solution and treatment method for aluminum and its alloys which forms a highly uniform thin coating, and provides a protective coating having a good appearance, corrosion resistance and paint adhesion.
2. Description of the Related Arts
Conventionally, aluminum and aluminum alloy surfaces were given with a chromate treatment or an alumite treatment. However, chromate treatment causes environmental pollution, is toxic to human health and generates waste sludge which cannot be disposed easily. On the other hand, alumite treatment requires heavy equipment, consumes much electric power and is uneconomical.
Various non-chromate treatment methods have been proposed to resolve these problems. For example, U.S. Pat. No. 4,148,670, entitled "Aqueous acidic conversion coating solution for aluminum" proposes acidic aqueous coatings solutions containing zirconium, titanium or mixtures of same, containing phosphates and fluorides, and having a pH within the range of approx. 1.5 -approx. 5.4.
Further, Japanese Patent Publication No. Sho 57-39314, entitled "Aluminum Surface Treatment Method", proposes a surface treatment for aluminum and its alloys using acidic aqueous solutions containing one, two or more titanium salts or zirconium salts having a concentration of 0.01-10 g/l as the metal, a peroxide concentration of 0.005-5 g/l, and one, two or more phosphoric acids or condensed phosphoric acids having a concentration of 0.05-20 g/l as phosphoric acid, these substances being present in a weight ratio of 1-10:0.1-10:1.5-30.
The aforesaid U.S. Pat. No. 4,148,670, "Aqueous acidic conversion coating solution for aluminum" and Japanese Patent Publication No. Sho 57-39314, "Aluminum Surface Treatment Method", may be used to form a protective coating on the surface of for example beverage containers made of aluminum or aluminum alloy.
Normally, beverage containers made of aluminum or aluminum alloy are manufactured by a processing technique known as drawing and ironing (DI process). During the processing operation, lubricating oil is applied to the metal surface, and aluminum powder (smat) is formed to adhere to the inner wall of the formed container. Therefore in general, prior to chemical treatment, the lubricating oil or smat must be removed from the metal surface, and after cleaning, the metal surface of the container is protected by the chemical treatment and coating.
In recent years, to reduce costs, there has been a trend to reduce the outer diameter of can lids from 206 (6.0 cm) to 204 (approx. 5.7 cm) and 202 (approx. 5.4 cm). The diameter of the upper part of the container must therefore also be reduced, and "necking" of the upper parts of cans after coating is now becoming an increasingly important issue. Therefore, higher paint adhesion is required for those cans of smaller diameter.
In the surface treatment solution used in the aforesaid Japanese Patent Publication No. Sho 57-39314, "Aluminum Surface Treatment Method", of the prior art, no attempt is made to remove the oxide film which forms on the metal surface by adding a certain chemicals, hence the chemical coating is formed over the oxide layer. The chemical coating is therefore formed unevenly over the oxide layer, and if it is attempted to give the can sufficient anti-corrosion properties such as resistance to boiling water or steam resistance properties (anti-retort properties), the thickness of the chemical coating must be increased. However when the thickness of the chemical coating is increased, adhesion between the coating and metal surface during the necking process, i.e. the paint adhesion, becomes insufficient. 0n the other hand, when it is attempted to provide sufficient paint adhesion by making the chemical coating thin, since the coating is uneven, the required anti-corrosion properties are not obtained.
The fluoride described in the aforesaid U.S. Pat. No. 4,148,670, "Aqueous acidic conversion coating solution for aluminum", etches the oxide layer on the metal surface and thereby removes it, however as there is no chemical to take up the oxygen in the oxide layer, the metal surface reoxidizes. The chemical coating is therefore once again formed over the oxide layer, and the coating is uneven as a result. If it is attempted to obtain corrosion resistance when the chemical coating is not sufficiently uniform, the chemical coating must be formed thicker and its adhesion becomes therefore poor. In order to achieve sufficient paint adhesion, the chemical coating must be made thinner, however as the coating is then uneven, its corrosion resistance is inadequate.
In other words, using the conventional surface treatment method, it was difficult to achieve the dual objectives of corrosion resistance and paint adhesion in the case of low diameter cans.
It is therefore an object of this invention to provide a surface treatment composition, treatment solution and treatment method for aluminum and its alloys, which forms a highly uniform thin coating, and provides a protective coating having a good appearance, corrosion resistance and paint adhesion.
To achieve the above objects, the surface treatment composition for aluminum and its alloys according to this invention comprises at least one type of phosphoric acid, condensed phosphoric acid or salt of these acids, at least one type of zirconium salt or titanium salt and a fluoride, further comprising at least one type of phosphorus acid, hypophosphorous acid or salt of these acids.
When a treatment solution is prepared by diluting the surface treatment composition for aluminum and its alloys with a suitable quantity of water so as to obtain a concentration within usable limits, and a chemical coating is formed (i.e. a surface treatment is performed) by this solution on a metal surface, the fluoride in the composition of this invention etches the oxide layer on the metal surface and thereby removes it from the surface. The phosphorous acid, hypophosphorous acid or salts of these acids in the composition of this invention act as reaction promoters. It is thought that they function as reducing agents which prevent oxidation of the bare aluminum surface. Due to the action of the zirconium salts and/or titanium salts, fluorides, phosphoric acids and/or condensed phosphoric acids, and phosphorous acids and/or hypophosphorous acids, a complex salt is formed due to which a strong coating is formed on the metal surface.
The surface treatment composition for aluminum and its alloys of this invention comprises at least one type of phosphoric acid, condensed phosphoric acid or salt of these acids, at least one type of zirconium salt or titanium salt and a fluoride, further comprising at least one type of phosphorus acid (H2 PHO3), hypophosphorous acid (HPH2 O2) or salt of these acids.
Examples of phosphoric acid or phosphates are H3 PO4, (NH4)H2 PO4, alkali metal phosphates such as NaH2 PO4, KH2 PO4, and alkaline earth metal phosphates such as calcium phosphate or magnesium phosphate. Examples of condensed phosphoric acids are pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid or ultraphosphoric acid, and examples of condensed phosphates are alkali metal salts such as those of sodium or potassium, alkaline earth metal salts such as those of calcium or magnesium, and ammonium salts.
Examples of zirconium salts are zirconium hydrofluoric acid (H2 ZrF6) and lithium, sodium, potassium or ammonium salts of fluorozirconium acid (Li2 ZrF6, Na2 ZrF6, K2 ZrF6, (NH4)2 ZrF6), zirconium sulfate (Zr(SO4)2), zirconyl sulfate (ZrO(S04), zirconium nitrate (Zr(NO3)4, zirconyl nitrate (ZrO(NO3)2, zirconium acetate or zirconium fluoride (ZrF4).
Examples of titanium salts are titanium hydrofluoric acid (H2 ZrF6) and lithium, sodium, potassium or ammonium salts of fluorotitanium acid (Li2 TiF6, Na2 TiF6, K2 TiF6, (NH4)2 TiF6), titanium sulfate (Ti(SO4)2), titanyl sulfate (TiO(SO4), titanium nitrate (Ti(NO3)4, titanyl nitrate (TiO(NO3)2, or titanium fluoride ( TiF3.TiF4).
Examples of fluorides are hydrofluoric acid (HF), ammonium fluoride (NH4 F), ammonium hydrofluoride (NH4 HF2), sodium fluoride (NaF) and sodium hydrogen fluoride (NaHF2).
Examples of phosphites and hypophosphites are alkali metal salts such as those of sodium or potassium, alkaline earth metal salts such as those of calcium or magnesium, and ammonium salts.
The surface treatment solution for aluminum and its alloys is obtained by diluting the aforesaid surface treatment composition with a suitable quantity of water so as to obtain a concentration within usable limits. The following description is based on this surface treatment solution (referred to hereafter simply as "treatment solution").
In a treatment solution according to this form of the invention, phosphoric acids, condensed phosphoric acids or salts of these acids, have a concentration of at least 10 ppm, preferably 10-500 ppm and more preferably 10-100 ppm expressed as PO4. When at least one type of phosphoric acids, condensed phosphoric acids or salts of these acids have a concentration in the treatment solution of less than 10 ppm expressed as PO4, blackening occurs on contact with boiling water. When on the other hand, phosphoric acids are excessive, not only does blackening occur on contact with boiling water but also the paint adhesion becomes poorer, hence it is desirable that their concentration is within 500 ppm as PO4.
In a treatment solution according to this invention, zirconium salts or titanium salts of which at least one type is present, have a concentration of at least 10 ppm, preferably 10-500 ppm and more preferably 10-100 ppm as the metal. When at least one type of zirconium salts or titanium salts have a concentration in the treatment solution of less than 10 ppm, the chemical coating is hardly formed. When on the other hand, zirconium salts, etc. are added in excess, an enhanced effect is not obtained, hence it is desirable that their concentration is within 500 ppm as the metal.
In a treatment solution according to this invention, effective fluorides have a concentration of at least 1 ppm and preferably 3-50 ppm as fluorine. When, in a treatment solution according to this invention, effective fluorides have a concentration of less than 1 ppm as fluorine, almost no etching of the aluminum surface occurs, so the adhesion between the surface of the aluminum and aluminum alloys and the coating deteriorates. When on the other hand, the fluoride content is excessive, the rate of etching is faster than that of coating formation so that it is difficult to form the coating, in addition to which blackening on contact with boiling water is worse and the paint adhesion deteriorates. It is therefore desirable that the concentration of fluorides is within 50 ppm as fluoride.
Herein, the term "effective fluoride" refers to a fluoride which releases fluoride ion in the treatment solution, the free fluoride ion (F-) in the solution hereafter being referred to as "effective fluoride ion". The concentration of this effective fluoride ion is found by measuring the solution using a meter having a fluoride ion electrode. Effective fluoride ion, in addition to etching the oxide layer on the aluminum surface, stops or prevents zirconium and/or titanium phosphate precipitates from forming in the treatment solution. It also complexes aluminum that has dissolved in the solution during surface treatment so that it does not have an adverse effect on the surface treatment process.
In a treatment solution according to this invention, phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, have a concentration in the treatment solution of at least 10 ppm, preferably 10-5000 ppm and more preferably 50-500 ppm as PO3 or hypophosphorous acid. When, in a treatment solution according to this invention, at least one type of phosphorous acids, hypophosphorous acids or salts of these acids have a concentration of less than 10 ppm as PO3 of hypophosphorous acid, the chemical coating is not sufficiently uniform. When on the other hand, the concentration of phosphorous acids or hypophosphorous acid in the solution exceeds 5000 ppm as PO3, the paint adhesion deteriorates.
Materials suitable for treatment by the surface treatment composition or treatment solution according to this invention, are aluminum and/or aluminum alloys. Examples of aluminum and/or aluminum alloys are aluminum, aluminum-copper, aluminum-zinc, aluminum-manganese, aluminum-magnesium, aluminum-magnesium-silicon or aluminum-zinc-magnesium. The invention may be applied to these materials in the form of sheet, rod, wire or pipe, or to beverage cans or the like.
A treatment solution in this invention is acidic. The pH of the treatment solution lies in the range 1.5-4.0, but more preferably 2.0-3.5. When the pH of the treatment solution is less than 1.5, etching is too severe, it is difficult to form the coating, blackening on contact with boiling water is worse and paint adhesion deteriorates. When on the other hand the pH of the treatment solution exceeds 4.0, the treatment solution becomes turbid and sludge forms. Moreover as the coating is hardly formed, blackening on contact with boiling water is worse.
The treatment temperature of the surface treatment method (referred to hereafter simply as "treatment method") lies in the range of room temperature -60°C, but preferably 30°-50°C When the treatment temperature is lower than room temperature (e.g. 25° C.), the coating forms slowly. When the treatment temperature exceeds 60°C, the treatment solution becomes turbid and sludge tends to form. Further, as a large quantity of energy is required to maintain the temperature, it is uneconomical.
The treatment time of the method according to this invention varies depending on the treatment composition, treatment temperature and treatment method, but it is generally of the order of 5-60 seconds. As examples of treatment methods according to this invention, aluminum products or the like may be immersed in the aforesaid treatment solution, or any method known in the art may be used such as spraying or coating the aforesaid treatment solution onto the aluminum products or the like.
Other preferred forms of the invention are described below.
(1) A surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of 10-500 ppm as PO4,
zirconium salts or titanium salts of which at least one type is present, having a concentration of 10-500 ppm as the metal,
effective fluorides having a concentration of 1-50 ppm as fluorine, and phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of 10-500 ppm as PO3 or hypophosphorous acid.
(2) A surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of 10-100 ppm as PO4,
zirconium salts or titanium salts of which at least one type is present, having a concentration of 10-100 ppm as the metal,
effective fluorides having a concentration of 3-50 ppm as fluorine, and
phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of 50-500 ppm as PO3 or hypophosphorous acid.
(3) A surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of 10-100 ppm as PO4,
zirconium salts or titanium salts of which at least one type is present, having a concentration of 10-100 ppm as the metal,
effective fluorides having a concentration of 3-20 ppm as fluorine, and
phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of 50-500 ppm as PO3 or hypophosphorous acid.
(4) A surface treatment method for aluminum and its alloys, wherein aluminum products are immersed in a surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of at least 10 ppm as PO4,
zirconium salts or titanium salts of which at least one type is present, having a concentration of at least 10 ppm as the metal,
effective fluorides having a concentration of at least 1 ppm as fluorine, and
phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of at least 10 ppm as PO3 or hypophosphorous acid.
(5) A surface treatment method for aluminum and its alloys, wherein aluminum products are immersed in a surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of 10-500 ppm as PO4,
zirconium salts or titanium salts of which at least one type is present, having a concentration of 10-500 ppm as the metal,
effective fluorides having a concentration of 1-50 ppm as fluorine, and
phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of 10-5000 ppm as PO3 or hypophosphorous acid.
(6) A surface treatment method for aluminum and its alloys, wherein aluminum products are immersed in a surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of 10-100 ppm as PO4,
zirconium salts or titanium salts of which at least one type is present, having a concentration of 10-100 ppm as the metal,
effective fluorides having a concentration of 3-50 ppm as fluorine, and
phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of 50-500 ppm as PO3 or hypophosphorous acid.
(7) A surface treatment method for aluminum and its alloys, wherein aluminum products are immersed in a surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of 10-100 ppm as PO4,
zirconium salts or titanium salts of which at least one type is present, having a concentration of 10-100 ppm as the metal,
effective fluorides having a concentration of 3-20 ppm as fluorine, and
phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of 50-500 ppm as PO3 or hypophosphorous acid.
(8) A surface treatment solution for aluminum and its alloys according to this invention of which the pH lies in the range 1.5-4∅
(9) A surface treatment solution for aluminum and its alloys used in the surface treatment method according to this invention, wherein the pH of the solution lies in the range of 1.5-4∅
(10) An aluminum product that has been immersed in a surface treatment solution for aluminum and its alloys according to this invention.
(11) An aluminum beverage container that has been immersed in a surface treatment solution for aluminum and its alloys according to this invention.
(12) An aluminum product that has been treated by the surface treatment method for aluminum and its alloys according to this invention.
(13) An aluminum beverage container that has been treated by the surface treatment method for aluminum and its alloys according to this invention.
(14) A surface treatment method for aluminum and its alloys according to this invention, wherein the treatment temperature lies in the range of room temperature -60°C
(15) A surface treatment method for aluminum and its alloys, wherein an aluminum product is immersed in a surface treatment solution for aluminum and its alloys comprising:
phosphoric acids, condensed phosphoric acids or salts of these acids, of which at least one type is present, having a concentration of 10-100 ppm as PO4,
zirconium fluoride having a concentration of 10-100 ppm as the Zr metal,
effective fluorides having a concentration of 3-20 ppm as fluorine, and
phosphorous acids, hypophosphorous acids or salts of these acids, of which at least one type is present, having a concentration of 50-500 ppm as PO3 or hypophosphorous acid.
FIG. 1 is a view in perspective showing a bent state of a test piece used in a paint adhesion test.
FIG. 2 is a view in perspective showing the bent test piece of FIG. 1 viewed from the rear.
FIG. 3 is a diagram describing a method of testing paint adhesion properties.
Next, the invention will be described in further detail with reference to specific examples.
(1) Object to be Treated
Container without a lid but with adhering lubricating oil and smat obtained by DI process of a 3004 alloy aluminum plate.
(2) Cleaner
Acidic cleaner of "Surfcleaner NHC 250" (Nippon Paint) was used.
(3) Treatment Conditions
The aforesaid container was sprayed with the above cleaner at 75°C for 60 seconds to remove lubricating oil and smat, and after being rinsed with tap water for 15 seconds, it was sprayed with the treatment solution shown in Table 1 and Table 2. Then, after being rinsed with tap water for 15 seconds and deionized water for 5 seconds, it was dried at 200° C. for 2 minutes.
(4) Cleaning Performance
Tests were carried out on the following items. The results are shown in Table 3.
(a) Blackening on Contact with Boiling Water
Bottom part of container cut out from a surface treated DI container (referred to hereafter as treated can) was immersed in boiling tap water at 100°C for 30 minutes, and the extent of blackening observed. Blackening was evaluated in the following 5 grades:
| ______________________________________ |
| ⊚ |
| No blackening |
| ∘ Slight blackening |
| Δ Some blackening |
| x Considerable blackening |
| x x Heavy blackening |
| ______________________________________ |
(b) Anti-retort Properties
A treated can was placed in steam at 125°C obtained by pressurizing tap water in a pressure pot, and the extent of whitening was observed. Whitening was evaluated in the following 5 grades:
| ______________________________________ |
| ⊚ |
| No whitening |
| ∘ Slight whitening |
| Δ Some whitening |
| x Considerable whitening |
| x x Heavy whitening |
| ______________________________________ |
(c) Paint Adhesion
A water-based white paint was applied on the external surface of a treated can, then a clear paint (epoxy acrylic clear paint) was applied on top, baked and dried to give a test piece. The paint adhesion was evaluated by the wedge bending method. The test piece was bent to an angle of 3' from a 0 mm diameter edge, as shown in FIG. 1, so that its diameter at 80 mm from this edge was 4 mm (FIG. 2). A tape was put over the bent part as shown in FIG. 3, then the tape was peeled off in the direction of the white arrow in FIG. 3, and the peeled length (mm) of paint film from the edge was measured. If the peeled paint length is shorter, the paint adhesion is better.
The test results are shown below.
| TABLE 1 |
| __________________________________________________________________________ |
| Zirconium salt or |
| Phosphoric acid or |
| Phosphorous acid or |
| titanium salt |
| condensed phosphate |
| hypophosphorous acid |
| Effective fluoride |
| Concen- Concen- Concen- Concen- Treatment |
| Treatment |
| tration tration tration tration temperature |
| time |
| Type |
| (Zr, Ti ppm) |
| Type (PO4, ppm) |
| Type (ppm) Type |
| (ppm) pH |
| (°C.) |
| (seconds) |
| __________________________________________________________________________ |
| Actual |
| 1 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 Phosphorous |
| 150 HF 10 2.8 |
| 45 20 |
| Example acids |
| 2 |
| H2 ZrF6 |
| 10 H3 PO4 |
| 4Q As above |
| 150 HF 10 2.8 |
| 50 30 |
| 3 |
| H2 ZrF6 |
| 100 H3 PO4 |
| 40 As above |
| 150 HF 10 2.8 |
| 35 15 |
| 4 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 10 As above |
| 150 HF 10 2.8 |
| 45 20 |
| 5 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 100 As above |
| 150 HF 10 2.8 |
| 45 20 |
| 6 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 As above |
| 50 HF 10 2.8 |
| 45 20 |
| 7 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 As above |
| 500 HF 10 2.8 |
| 45 20 |
| 8 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 As above |
| 150 HF 3 2.8 |
| 45 20 |
| 9 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 As above |
| 150 HF 20 2.8 |
| 45 20 |
| 10 |
| H2 ZrF6 |
| 10 H3 PO4 |
| 10 As above |
| 50 HF 3 2.8 |
| 50 30 |
| 11 |
| H2 ZrF6 |
| 100 H3 PO4 |
| 100 As above |
| 500 HF 20 2.8 |
| 35 15 |
| 12 |
| H2 ZrF4 |
| 40 H3 PO4 |
| 40 As above |
| 150 HF 10 2.8 |
| 45 20 |
| 13 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 As above |
| 150 HF 10 3.3 |
| 45 20 |
| 14 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 hypophos- |
| 150 HF 10 2.8 |
| 45 20 |
| phorous |
| acids |
| 15 |
| H2 ZrF6 |
| 40 Na5 P2 O7 |
| 40 Phosphorous |
| 150 HF 10 2.8 |
| 45 20 |
| acids |
| 16 |
| H2 ZrF6 |
| 40 Na7 P3 O10 |
| 40 As above |
| 150 HF 10 2.8 |
| 45 20 |
| 17 |
| H2 TiF6 |
| 40 H3 PO4 |
| 40 As above |
| 150 HF 10 2.8 |
| 45 20 |
| 18 |
| H2 ZrF6 |
| 20 H3 PO4 |
| 40 As above |
| 150 HF 10 2.8 |
| 45 20 |
| h2 TiF6 |
| __________________________________________________________________________ |
| TABLE 2 |
| __________________________________________________________________________ |
| Zirconium salt or |
| Phosphoric acid or |
| Phosphorous acid or |
| titanium salt |
| condensed phosphate |
| hypophosphorous acid |
| Effective fluoride |
| Concen- Concen- Concen- Concen- Treatment |
| Treatment |
| tration tration tration tration temperature |
| time |
| Type |
| (Zr, Ti ppm) |
| Type (PO4, ppm) |
| Type (ppm) Type |
| (ppm) pH |
| (°C.) |
| (seconds) |
| __________________________________________________________________________ |
| Comparison |
| 1 |
| H2 ZrF6 |
| 40 H2 PO4 |
| 40 -- -- HF 10 2.8 |
| 45 20 |
| Example |
| 2 |
| H2 ZrF6 |
| 100 H3 PO4 |
| 40 -- -- HF 10 2.8 |
| 45 20 |
| 3 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 100 -- -- HF 10 2.8 |
| 45 20 |
| 4 |
| -- -- H2 PO4 |
| 40 Phosphorous |
| 150 HF 10 2.8 |
| 45 20 |
| acids |
| 5 |
| H2 ZrF6 |
| 40 -- -- As above |
| 150 HF 10 2.8 |
| 45 20 |
| 6 |
| H2 ZrF6 |
| 40 H3 PO4 |
| 40 As above |
| 150 -- -- 2.8 |
| 45 20 |
| __________________________________________________________________________ |
| TABLE 3 |
| ______________________________________ |
| Blackening on Paint |
| contact with |
| Anti-retort |
| adhesion |
| boiling water |
| properties |
| (mm) |
| ______________________________________ |
| Actual Example |
| 1 ⊚ |
| ⊚ |
| 25 |
| 2 ⊚ |
| ∘ |
| 21 |
| 3 ⊚ |
| ⊚ |
| 27 |
| 4 ⊚ |
| ∘ |
| 22 |
| 5 ⊚ |
| ⊚ |
| 28 |
| 6 ⊚ |
| ∘ |
| 22 |
| 7 ⊚ |
| ⊚ |
| 29 |
| 8 ⊚ |
| ⊚ |
| 24 |
| 9 ⊚ |
| ⊚ |
| 25 |
| 10 ⊚ |
| ∘ |
| 23 |
| 11 ⊚ |
| ⊚ |
| 30 |
| 12 ⊚ |
| ⊚ |
| 26 |
| 13 ⊚ |
| ∘ |
| 24 |
| 14 ⊚ |
| ⊚ |
| 26 |
| 15 ⊚ |
| ⊚ |
| 25 |
| 16 ⊚ |
| ⊚ |
| 26 |
| 17 ⊚ |
| ⊚ |
| 24 |
| 18 ⊚ |
| ⊚ |
| 23 |
| Comparative example |
| 1 ⊚ |
| Δ 37 |
| 2 ⊚ |
| ⊚ |
| 50 |
| 3 ⊚ |
| ⊚ |
| 48 |
| 4 x x x x 22 |
| 5 x x x x 27 |
| 6 x x x x 23 |
| ______________________________________ |
As described heretofore, according to the surface treatment composition, surface treatment solution and surface treatment method of this invention, a highly uniform thin coating is formed, hence machining and adhesion properties are far superior to those obtained using conventional techniques, and this protective coating also provides excellent resistance to blackening on contact with boiling water and anti-retort properties.
Ikeda, Satoshi, Kamimura, Masayuki
| Patent | Priority | Assignee | Title |
| 6200693, | May 22 1997 | Henkel Corporation | Water-based liquid treatment for aluminum and its alloys |
| 6419731, | Apr 20 2000 | NIPPON PAINT CO , LTD | Nonchromate rust preventive agent for aluminum, method of rust prevention and rust-preventive aluminum products |
| 6524403, | Aug 23 2001 | CITIBANK, N A | Non-chrome passivation process for zinc and zinc alloys |
| 6860687, | Dec 08 1998 | Newfrey LLC | Weldable aluminum stud |
| 7714414, | Nov 29 2004 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method and apparatus for polymer dielectric surface recovery by ion implantation |
| 7758967, | Apr 27 2007 | Stanley Electric Co., Ltd. | Antirust treatment method for an aluminum die-cast part for vehicular lighting fixture, and an aluminum die-cast part for vehicular lighting fixture |
| 7879157, | Dec 12 2003 | Newfrey LLC | Method for pretreating the surfaces of weld parts of aluminum or alloys thereof and corresponding weld parts |
| 8007576, | Dec 03 2007 | Ya Thai Chemical Co., Ltd. | Chrome-free corrosion inhibitor composition |
| 8097093, | Sep 28 2007 | PPG Industries Ohio, Inc | Methods for treating a ferrous metal substrate |
| 8652270, | Sep 28 2007 | PPG Industries Ohio, Inc. | Methods for treating a ferrous metal substrate |
| 9273399, | Mar 15 2013 | PPG Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
| 9347134, | Jun 04 2010 | PRC-DESOTO INTERNATIONAL, INC | Corrosion resistant metallate compositions |
| 9428410, | Mar 06 2013 | PPG Industries Ohio, Inc. | Methods for treating a ferrous metal substrate |
| Patent | Priority | Assignee | Title |
| 4148670, | Apr 05 1976 | AMCHEM PRODUCTS, INC A CORP OF DEL | Coating solution for metal surface |
| 4264378, | Feb 14 1979 | METALLGESELLSCHAFT A G , REUTERWEG 14, D-6000 FRANKFURT AM MAIN 1, FEDERAL REPUBLIC OF GERMANY, A CORP OF THE FEDERAL REPUBLIC OF GERMANY | Chromium-free surface treatment |
| 5449415, | Jul 30 1993 | Henkel Corporation | Composition and process for treating metals |
| EP15020, | |||
| FR1172741, | |||
| GB2250025, | |||
| JP5739314, | |||
| WO9504169, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Nov 01 1996 | IKEDA, SATOSHI | NIPPON PAINT CO , LTD | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 008347 | /0930 | |
| Nov 01 1996 | KAMIMURA, MASAYUKI | NIPPON PAINT CO , LTD | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 008347 | /0930 | |
| Nov 18 1996 | Nippon Paint Co., Ltd. | (assignment on the face of the patent) | / |
| Date | Maintenance Fee Events |
| Feb 25 1999 | ASPN: Payor Number Assigned. |
| Aug 30 2001 | M183: Payment of Maintenance Fee, 4th Year, Large Entity. |
| Aug 26 2005 | M1552: Payment of Maintenance Fee, 8th Year, Large Entity. |
| Aug 19 2009 | M1553: Payment of Maintenance Fee, 12th Year, Large Entity. |
| Date | Maintenance Schedule |
| Mar 17 2001 | 4 years fee payment window open |
| Sep 17 2001 | 6 months grace period start (w surcharge) |
| Mar 17 2002 | patent expiry (for year 4) |
| Mar 17 2004 | 2 years to revive unintentionally abandoned end. (for year 4) |
| Mar 17 2005 | 8 years fee payment window open |
| Sep 17 2005 | 6 months grace period start (w surcharge) |
| Mar 17 2006 | patent expiry (for year 8) |
| Mar 17 2008 | 2 years to revive unintentionally abandoned end. (for year 8) |
| Mar 17 2009 | 12 years fee payment window open |
| Sep 17 2009 | 6 months grace period start (w surcharge) |
| Mar 17 2010 | patent expiry (for year 12) |
| Mar 17 2012 | 2 years to revive unintentionally abandoned end. (for year 12) |